Iodine detergent compositions



United States Patent 3,277,010 IODINE DETERGENT COMPOSITIONS Leslie M.Schenck, Mountainside, and Harry Kaplan, Westfield, N.J., assignors toGeneral Aniline & Film Corporation, New York, N.Y., a corporation ofDelaware N0 Drawing. Filed June 26, 1963, Ser. No. 290,639 7 Claims.(Cl. 252106) This invention relates generally to iodine detergentcomposiitons and, more particularly, to novel compositions comprisingiodine and halides of various liquid nonionic polyglycol ether typesurface active agents.

As is well known in the art, liquid nonionic polyglycol ether typesurface active agents obtained by condensing alkaline oxides with waterinsoluble organic compounds containing at least 6 carbon atoms andhaving an active hydrogen are capable of readily dissolving iodine toyield germicidal-detergent compositions. After appropriate compoundingwith Water and a sufficient amount of acid to obtain a pH of at leastabout or lower, these compositions have been shown to be particularlyeffective for use in various apparatus for washing milk bottles, beerbottles and like containers for catable products and for cleaningapparatus and equipment concerned in the manufacture and transport ofsuch products. However, although these compositions possess excellentdetergent and germicidal characteristics, they suffer from thedisadvantage of producing a relatively high level of foam which detractsfrom their overall efficiency and economy in commercial cleaning andsanitizing operations. It should be immediately apparent that excessivefoaming in a clean-ing compound affects its ability to adequately cleanthe container being so treated and also poses a potential danger to thevarious mechanical equipment employed in commercial cleaning andsanitizing operations.

Accordingly, it is the primary object of this invention to provide anovel iodine detergent composition possessing the desirable germicidalproperties and detergent characteristics of the prior art compositionsformulated from liquid nonionic polyglycol ether type surfactants butwithout the disadvantage of having excessive foaming characteristics.

It is still another object of this invention to provide a novelcomposition of matter comprising iodine and a chlorine containingnonionic surface active composition having excellentgermicidal-detergent characteristics as well as low foamingcharacteristics.

It has now been found that the above objectives can be obtained byformulating a germicide-detergent composition from iodine and varioushalide containing nonionic surface active compositions. Quiteunexpectedly, it has been found that if certain halide containingnonionic surface active agents are employed for formulating the novelcompositions of this invention a composition results which has extremelylow foaming properties along with the expected gerrnicide and detergentproperties.

The nonionic surface active agents which are employed to prepare thenovel compositions of this invention are halides of polyethoxylatedphenols and polyethoxylated aliphatic alcohols characterized by thefollowing general formula:

wherein R represents either an alkyl group containing 8 to 22 carbonatoms or a phenyl or naphthyl substituted in the ring with 1, 2 or 3alkyl groups having a total of from 6 to 36 carbon atoms; R representshydrogen, methyl, or ethyl; n represents a positive integer of from3,277,010 Patented Oct. 4, 1966 2 to 12 inclusive and X representschlorine, bromine or iodine. The above compositions are known in the artand are generally prepared by converting any polyethoxylated phenol orpolyethoxylated aliphatic alcohol to the corresponding halide byconventional means. The prep-aration of polyethoxylated phenols andpolyethoxylated aliphatic alcohols upon which the above halides arebased are described in great detail in U.S. Patents 1,970,578,2,213,477, 2,575,832, 2,593,112, and 2,676,975. The correspondinghalides and methods for their preparation are disclosed in U.S. Patents2,249,111, 2,098,203, 2,097,441, 2,097,411, 2,209,911 and 3,061,552, thecomplete disclosures and teachings of which are incorporated herein byreference thereto.

The novel compositions of this invention are prepared simply by addingelemental iodine to the halogen containing surfactants above describedat a temperature ranging from about 20 C. to 100 C. and agitating forperiods of times ranging from 10 to 20 minutes. However, particularlyeffective results have been obtained when the elemental iodine was addedat temperatures ranging from 40 C. to C. and agitation was carried outfor periods of time ranging from 2 to 6 hours.

The amount of elemental iodine which is added to the halides ofpolyethoxylated phenols and polyethoxylated aliphatic alcohols is notnarrowly critical but it is preferred to add suflicient iodine so as toprovide from 1 to 30% by weight of available iodine with from 10 to 22%by weight available iodine being particularly preferred.

Germicidal cleansing solutions may be formulated from the iodinecontaining surface active agents in a conventional manner, mostfrequently by the addition of an acid such as phosphoric acid orhydrochloric acid and Water.

As has heretofore been pointed out, the novel compositions of thisinvention are prepared by adding elemental iodine to a specific class ofhalides of polyethoxylated phenols and polyethoxylated aliphaticalcohols. It should be immediately apparent that the surface activeagents employed to formulate the novel compositions of the instantinvention differ from the polyethoxylated phenols and polyethoxylatedaliphatic alcohols heretofore proposed not only by the fact that theyhave a terminal halogen atom -in place of the terminal hydroxyl group ofthe prior art compounds, but also due to the fact that the compositionshave only from 2 to 12 recurring oxyalkylene units. It should be pointedout that if halogen-containing nonionic surface active agents areemployed having more than 12 recurring oxyalkylene units, compositionswill be obtained which have effective detergent and germicidalproperties as would be expected but that these compositions will have nobetter foaming properties than similar compositions prepared fromnonionic surface active agents containing terminal hydroxyl groups.Therefore, the heart of the instant invention involves the use ofnonionic surface active agents having terminal halide atoms and from 2to 12 recurring oxyalkylene units.

The examples will' now illustrate the best mode contemplated forcarrying out the invention but it is to be understood that it is notintended to be limited thereto.

Example 1 One hundred forty-four parts by weight of a halogenatedsurface active agent of the following formula:

C,HQQ(O 0112011912 01 4H9 and 56 parts by weight of iodine were mixedtogether at Foam height of halogenated base, millimeters 20 Foam heightof non-halogenated base, millimeters 22 From the above it can be seenthat there is no substantial difference in foam height when using ahalogenated as opposed to a non-halogenated surface active agent. It canbe seen that in this instance the number of recurring oxyalkylene unitswas 125.

Example 2 One hundred forty-four parts by weight of a halogenatedsurface active agent. It can be seen that in this instance the number ofrecurring oxyalkylene units was 125.

One hundred forty-four parts by weight of a halogenated surface activeagent of the following formula:

1z 2Q(O C HiOHzl 4 and 56 parts by weight of iodine were mixed togetherat 90 C. for 0.5 hour to yield 200 parts by weight of the product having22.3 weight percent of available iodine.

A foam comparison between the product obtained according to the aboveprocedure and the corresponding non-halogenated base was carried out inthe exact manner as set forth in Example 1 with the following results:

Foam height of halogenated base, millimeters 8 Foam height ofnon-halogenated base, millimeters 26 From the above example it can beseen that more than a 300% reduction in foam occurred by using thecorresponding halide derivative. It is also pointed out that in thisexample the composition employed had 4 recurring oxyethylene units.

Example 3 One hundred seventy-four parts by weight of a halogenatednonionic surface active agent of the formula:

CH (OCH OHMsoCI and 26 parts by weight of iodine were mixed together at'80" C. and agitated for four hours to yield 200 parts by weight of acomposition having 10.1% available iodine.

Comparison of the above composition with the correspondingnon-halogenated derived material in accordance with the procedure ofExample 1 yielded the following results:

Foam height of halogenated base, millimeters 24 Foam height ofnon-halogenated base, millimeters 22 From the above results it can beseen that in this instance the foam produced was even greater than thefoam resulting from the corresponding non-halogenated base. It can beseen that the composition employed in this example had 130 recurringoxyalkylene units.

4 Example 4 Two hundred parts by weight of a halogenated nonionicsurface active agent of the following formula:

@ 0 CHzCHc) 1013:

and 85 parts by weight of iodine were mixed together at 70 C. andagitated for 12 hours to yield 285 parts by weight of. acomposit-ionhaving 23.8% of available iodine.

Comparison with the composition made from the correspondingnon-halogenated surface active agent in ac cordance with the procedureof Example 1 had the following results:

Foam height of halogenated base, millimeters 7 Foam height ofnon-halogenated base, millimeters 28 From the above it can be seen thatalmost a 400% reduction in foam occurred when using the halogenatednonionic surface active agent. It is also pointed out that in thisinstance there were present 10 recurring oxyethylene units in thehalogenated base.

Example 5 One hundred fifty-two parts by weight of a halogenatednonionic surface active agent of the (following formula:

@ 0 omonmol Ctr Hi9 and 48 parts by weight of iodine were mixed togetherat 60 C. and agitated for 3 hours to yield 200 parts by weight of acomposition having 16.2% of available iodine.

Comparison of foam with an iodine composition prepared from thecorresponding non-halogenated base yielded the following results:

Foam height of halogenated base, millimeters 10 Foam height ofnon-halogenated base, millimeters 30 From the above results it can beseen that the 200% reduction in foam occurred in this instance.

Example 6 One hundred sixty-five parts by weight of a halogenatednonionic surface active agent of the following formula:

(OCHztiiHhI 1:11:: and 58 parts by weight of iodine were mixed at 50 C.and agitated for 4 hours to yield 223 parts by weight of a compositionhaving 20.0% of available iodine.

Comparison of the foam produced by this composition with one preparedfrom the corresponding non-halogenated base yielded the followingresults:

Foam height of halogenated base, millimeters 8 Foam height ofnon-halogenated base, millimeters 25 From the above it can be seen thatagain more than a 300% reduction inrfoam occurred when using thehalogenated base.

Example 7 Two hundred parts by weight of a halogenated nonionic surfaceactive agent of the formula:

C1H5 Cs x1(O CHnHhI and parts by weight of iodine were mixed together at40 C. and stirred for 10 hours to yield 280 parts by weight of acomposition having 24.8% of available iodine.

Comparison of the foaming characteristics of the above product with oneprepared from the corresponding nonhalogenated base yielded thefollowing results:

Foam height of halogenated base, millimeters Foam height ofnon-halogenated base, millimeters From the above example it can be seenthat a 200% reduction in foam occurred.

Example 8 Two hundred parts by weight of a halogenated nonionic surfaceactive agent of the following formula:

and 30 parts by weight of iodine were mixed together at 30 C. andstirred for 6 hours to yield 230 parts by weight of a composition having11.4% of available iodine.

Comparison of the foam characteristics of the above product with the oneprepared from the corresponding non-halogenated base had the followingresults:

Foam height of halogenated base, millimeters 28 Foam height ofnon-halogenated base, millimeters 26 From the above results .it can beseen that in this instance the iodine composition prepared from thehalogenated nonionic surface active agent produced more foam than theone prepared from the resulting non-halogenated base. It should be notedthat in this instance the composition contained 40 recurring oxyalkyleneunits.

Example 9 Two hundred parts by Weight of a halogenated nonionic surfaceactive agent of the following formula:

and 56 parts by weight of iodine were mixed together at 20 C. andstirred for 5 hours to yield 256 parts by weight of a composition having16.4% available iodine.

Comparison of the foaming characteristics of the above product with oneprepared from the corresponding nonhalogenated base yielded thefollowing:

Foam height of halogentated base, millimeters 30 Foam height ofnon-halogenated base, millimeters 32 From the above data it can be seenthat the compound prepared from the halogenated nonionic agent hadsubstantially the same foaming characteristics as one prepared from thenon-halogenated surface active agent. It should be noted that in thisinstance the nonionic surface active agent employed had 120 recurringoxyal kylene units.

Example 10 One hundred forty-four parts by weight of a nonionic surfaceactive agent of the following formula:

Ow OHzCH2)15oCl and 56 parts by weight of iodine were mixed at 80 C. andstirred for 6 hours to yield 200 parts by weight of a composition having24.6% available iodine.

Comparison of foaming characteristics of the above composition with oneprepared from the corresponding non-halogenated base yielded thefollowing results:

Foam height of halogenated base, millimeters 32 Foam height ofnon-halogenated base, millimeters 36 From the above example, it canagain be seen that in this instance the results obtained from thehalogenated derivative were substantially the same as thenon-halogenated one. It is again noted that the halogenated nonionicsurface active agent employed in this example had recurring oxyalkyleneunit-s.

Many modifications and variations of the above examples will occur tothose skilled in the art such as employing compounds mentioned in thespecification for those mentioned in the specific examples. Therefore,it

' is not intended that this invention be limited except as wherein Rrepresents a radical selected from the group consisting of alkylradicals of from 8 to 22 carbon atoms, phenyl and naphthyl radicalssubstituted with from 1 to 3 a lkyl groups having a total of from 6 to36 carbon atoms, R is selected from the group consisting of hydrogen,methyl and ethyl, n represents a positive integer of from 2 to 12 and Xrepresents a halogen selected from the group consisting of chlorine,bromine and iodine.

3. The composition as defined in claim 1 wherein the halide of thenonionic surface active agent has the formula:

CIZHZSQU) CHzOH2)4C 4. The composition as defined in claim 1 wherein thehalide of the nonionic surface active agent has the formula:

@womommm C is s7 5. The composition as defined in claim 1 wherein thehalide of the nonionic surface active agent has the formula:

@ oomorrmm 6. The composition as defined in claim 1 wherein the halideof the nonionic surface active agent has the formula:

7. The composition as defined in claim .1 wherein the halide of thenonionic surface active agent has the formula:

References Cited by the Examiner UNITED STATES PATENTS Bruson et a1.260-613 Britton et a1. 260-613 Hosmer et a1. 252F406 XR Winicov et a1260-613 Schenck et a1. 252'156 XR 8 FOREIGN PATENTS 703,091 1/1954 GreatBritain.

LEON D. ROSDOL, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,277,010 October 4, 1966 Leslie M. Schenck et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 3, lines 22 to 24, strike out "One hundred fortyfour parts byweight of a halogenated surface active agent. It can be seen that inthis instance the number of recurring oxyalkylene units was l2S."-column 6, line 48, the right-hand portion of the formula should read asshown below instead of as in the patent;

-(OCH CH Br Signed and sealed this 5th day of September 1967.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A WATER-SOLUBLE, LOW-FOAMING GERMICIDAL-DETERGENT COMPOSITIONCONSISTING ESSENTIALLY OF (A) THE HALIDE OF A NONIONIC SURFACE ACTIVEAGENT SELECTED FROM THE CLASS CONSISTING OF POLYETHOXYLATED PHENOLS ANDPOLYETHOXYLATED AALIPHATIC ALCOHOLS HAVING FROM 2 TO 12 RECURRINGOXYALKYLENE UNIT AND, (B) ELEMENTAL IODINE IN AN AMOUNT SUFFICIENT TOPROVIDE FROM ABOUT 1 TO 30% BY WEIGHT AVAILBLE IODINE IN SAIDCOMPOSITION.